CA2590082A1 - Processes for the preparation and purification of hydroxymethylfuraldehyde and derivatives - Google Patents
Processes for the preparation and purification of hydroxymethylfuraldehyde and derivatives Download PDFInfo
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- CA2590082A1 CA2590082A1 CA002590082A CA2590082A CA2590082A1 CA 2590082 A1 CA2590082 A1 CA 2590082A1 CA 002590082 A CA002590082 A CA 002590082A CA 2590082 A CA2590082 A CA 2590082A CA 2590082 A1 CA2590082 A1 CA 2590082A1
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- Prior art keywords
- hydroxymethyl
- fructose
- organic solvent
- reaction mixture
- furaldehyde
- Prior art date
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- 238000000034 method Methods 0.000 title claims abstract 47
- 238000002360 preparation method Methods 0.000 title abstract 7
- CETXOEGRUBXUAL-UHFFFAOYSA-N 3-(hydroxymethyl)furan-2-carbaldehyde Chemical compound OCC=1C=COC=1C=O CETXOEGRUBXUAL-UHFFFAOYSA-N 0.000 title 1
- 238000000746 purification Methods 0.000 title 1
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims abstract 28
- 229930091371 Fructose Natural products 0.000 claims abstract 22
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims abstract 22
- 239000005715 Fructose Substances 0.000 claims abstract 22
- 239000003960 organic solvent Substances 0.000 claims abstract 19
- DSLRVRBSNLHVBH-UHFFFAOYSA-N 2,5-furandimethanol Chemical compound OCC1=CC=C(CO)O1 DSLRVRBSNLHVBH-UHFFFAOYSA-N 0.000 claims abstract 12
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 claims abstract 8
- 239000003377 acid catalyst Substances 0.000 claims abstract 8
- 229940040102 levulinic acid Drugs 0.000 claims abstract 4
- 239000000203 mixture Substances 0.000 claims 18
- 239000011541 reaction mixture Substances 0.000 claims 17
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims 9
- 239000002202 Polyethylene glycol Substances 0.000 claims 8
- 229920001223 polyethylene glycol Polymers 0.000 claims 8
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 claims 7
- 239000003456 ion exchange resin Substances 0.000 claims 7
- 229920003303 ion-exchange polymer Polymers 0.000 claims 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims 6
- 238000006297 dehydration reaction Methods 0.000 claims 6
- 238000010438 heat treatment Methods 0.000 claims 6
- 230000002378 acidificating effect Effects 0.000 claims 5
- 239000003054 catalyst Substances 0.000 claims 5
- 239000002904 solvent Substances 0.000 claims 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims 3
- 239000002253 acid Substances 0.000 claims 3
- 229920001429 chelating resin Polymers 0.000 claims 3
- 239000012074 organic phase Substances 0.000 claims 3
- 239000012071 phase Substances 0.000 claims 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims 2
- 238000001704 evaporation Methods 0.000 claims 2
- 230000008020 evaporation Effects 0.000 claims 2
- 239000012628 flowing agent Substances 0.000 claims 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims 2
- 235000019534 high fructose corn syrup Nutrition 0.000 claims 2
- 229940043265 methyl isobutyl ketone Drugs 0.000 claims 2
- 230000003472 neutralizing effect Effects 0.000 claims 2
- 238000000638 solvent extraction Methods 0.000 claims 2
- YZUPZGFPHUVJKC-UHFFFAOYSA-N 1-bromo-2-methoxyethane Chemical compound COCCBr YZUPZGFPHUVJKC-UHFFFAOYSA-N 0.000 claims 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims 1
- QYRHWHTUPKYDRQ-UHFFFAOYSA-N 4-hydroxy-3-methylfuran-2-carbaldehyde Chemical compound CC=1C(O)=COC=1C=O QYRHWHTUPKYDRQ-UHFFFAOYSA-N 0.000 claims 1
- CCDRPZFMDMKZSZ-UHFFFAOYSA-N 5-(ethoxymethyl)furan-2-carbaldehyde Chemical compound CCOCC1=CC=C(C=O)O1 CCDRPZFMDMKZSZ-UHFFFAOYSA-N 0.000 claims 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 claims 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims 1
- 229910021536 Zeolite Inorganic materials 0.000 claims 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims 1
- 239000003463 adsorbent Substances 0.000 claims 1
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 239000008346 aqueous phase Substances 0.000 claims 1
- 125000003118 aryl group Chemical group 0.000 claims 1
- 125000000753 cycloalkyl group Chemical group 0.000 claims 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims 1
- 239000010408 film Substances 0.000 claims 1
- 229910052500 inorganic mineral Inorganic materials 0.000 claims 1
- 239000000463 material Substances 0.000 claims 1
- 239000011707 mineral Substances 0.000 claims 1
- 239000002808 molecular sieve Substances 0.000 claims 1
- 229910052759 nickel Inorganic materials 0.000 claims 1
- 238000000526 short-path distillation Methods 0.000 claims 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims 1
- 239000011949 solid catalyst Substances 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 claims 1
- 239000010409 thin film Substances 0.000 claims 1
- 239000010457 zeolite Substances 0.000 claims 1
- 229910052726 zirconium Inorganic materials 0.000 claims 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/42—Singly bound oxygen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
- C07C51/245—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of keto groups or secondary alcohol groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D307/38—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D307/40—Radicals substituted by oxygen atoms
- C07D307/46—Doubly bound oxygen atoms, or two oxygen atoms singly bound to the same carbon atom
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Furan Compounds (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Paints Or Removers (AREA)
- Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
Abstract
The present application discloses: A method for the preparation of 2,5-(hydroxymethyl)furaldehyde from fructose with specific organic solvents. A
method for the preparation of 2,5-(hydroxymethyl)furaldehyde from fructose with an acid catalyst. A method for the preparation of 2,5-(hydroxymethyl)furaldehyde from fructose with a with a two-phase organic solvent system. A method for the preparation of a 2,5-(hydroxymethyl)furaldehyde derivative from fructose. A method for the preparation of levulinic acid from fructose. A method for the preparation of 2,5-bis-(hydroxymethyl)furan from 2,5-(hydroxymethyl)furaldehyde.
method for the preparation of 2,5-(hydroxymethyl)furaldehyde from fructose with an acid catalyst. A method for the preparation of 2,5-(hydroxymethyl)furaldehyde from fructose with a with a two-phase organic solvent system. A method for the preparation of a 2,5-(hydroxymethyl)furaldehyde derivative from fructose. A method for the preparation of levulinic acid from fructose. A method for the preparation of 2,5-bis-(hydroxymethyl)furan from 2,5-(hydroxymethyl)furaldehyde.
Claims (38)
1. A method of preparing 2,5 -(hydroxymethyl)furaldehyde comprising:
i) combining a fructose source, a solvent selected from the group consisting of 1-methyl-2-pyrrolidinone, dimethylacetamide, dimethylformamide and combinations of thereof, with a catalyst to provide a reaction mixture;
ii) heating said reaction mixture to a temperature and for a time sufficient to promote an acid-catalyzed dehydration reaction of fructose in said fructose source to form a product mixture; and iii) isolating 2,5-(hydroxymethyl)furaldehyde from said product mixture.
i) combining a fructose source, a solvent selected from the group consisting of 1-methyl-2-pyrrolidinone, dimethylacetamide, dimethylformamide and combinations of thereof, with a catalyst to provide a reaction mixture;
ii) heating said reaction mixture to a temperature and for a time sufficient to promote an acid-catalyzed dehydration reaction of fructose in said fructose source to form a product mixture; and iii) isolating 2,5-(hydroxymethyl)furaldehyde from said product mixture.
2. The method of claim 1 wherein said fructose source is comprised of high fructose corn syrup.
3. The method of claim 1 wherein said acid-catalyzed dehydration reaction is carried out under vacuum and temperature conditions sufficient to remove water from the reaction mixture.
4. The method of claim 1 wherein said reaction mixture further includes a water absorbing molecular sieve material.
5. The method of claim 1 wherein said catalyst is selected from the group consisting of a mineral acid, an acidic ion-exchange resin, and a zeolite.
6. The method of claim 1 wherein said catalyst is a solid catalyst comprised of a strong acid ion exchange resin.
7. The method of claim 6 wherein said strong acid ion-exchange resin catalyst is selected from the group consisting of Amberlyst 35, Amberlyst 36, Amberlyst 15, Amberlyst 131, Lewatit S2328, Lewatit K2431, Lewatit S2568, Lewatit K2629, Dianion SK104, Dianion PK228, Dianion RCP160, and Relite RAD/F.
8. The method of claim 1 wherein said reaction mixture is heated to a temperature of from about 95° C to about 125° C.
9. The method of claim 1 wherein said reaction mixture is heated to a temperature of from about 105° C to about 115° C.
10. The method of claim 1 wherein said reaction mixture is heated for a time period of about one to about six hours.
11. A method of preparing 2,5 - (hydroxymethyl)furaldehyde comprising:
i) combining a fructose source, an organic solvent, and an acid catalyst to provide a reaction mixture;
ii) heating said reaction mixture to a temperature and for a time sufficient to promote a dehydration reaction of fructose in said fructose source to form a first product mixture;
iii) neutralizing the pH of the first product mixture to a pH of about 7 to 9;
iv) distilling the first product mixture after neutralizing the pH to remove said organic solvent remaining in the first product mixture; and v) purifying said product mixture to provide a second product mixture comprising greater than 60% by weight of 2,5-(hydroxymethyl)furaldehyde.
i) combining a fructose source, an organic solvent, and an acid catalyst to provide a reaction mixture;
ii) heating said reaction mixture to a temperature and for a time sufficient to promote a dehydration reaction of fructose in said fructose source to form a first product mixture;
iii) neutralizing the pH of the first product mixture to a pH of about 7 to 9;
iv) distilling the first product mixture after neutralizing the pH to remove said organic solvent remaining in the first product mixture; and v) purifying said product mixture to provide a second product mixture comprising greater than 60% by weight of 2,5-(hydroxymethyl)furaldehyde.
12. The method of claim 11 wherein said fructose source is comprised of high fructose corn syrup.
13. The method of claim 11 wherein said second product mixture comprises greater than 75% by weight of 2,5-(hydroxymethyl)furaldehyde.
14. The method of claim 11 wherein purifying said product isolate comprises a solvent extraction process.
15. The method of claim 14 wherein said solvent extraction process comprises:
(i) adding a mixture comprising a water-immiscible organic solvent and water to said product isolate to provide an organic phase and an aqueous phase;
(ii) recovering said organic phase; and (iii) removing said water-immiscible organic solvent from the recovered organic phase to yield purified HMF.
(i) adding a mixture comprising a water-immiscible organic solvent and water to said product isolate to provide an organic phase and an aqueous phase;
(ii) recovering said organic phase; and (iii) removing said water-immiscible organic solvent from the recovered organic phase to yield purified HMF.
16. The method of claim 15 wherein said water-immiscible organic solvent is selected from the group consisting of ethyl acetate, methyl isobutylketone, methyl ethyl ketone, methyl t-butyl ether, octanol, pentanol, butyl acetate, and combinations thereof.
17. The method of claim 11 wherein the acid catalyst is an acidic ion exchange resin and the acidic ion exchange resin is removed from the first reaction mixture prior to the act of distilling.
18. The method of claim 11 further comprising adding a non-volatile flowing agent to first product mixture prior to the act of distilling.
19. The method according to claim 18 wherein said non-volatile flowing agent is selected from the group consisting of polyethylene glycol, polyethylene glycol monoether, polyethylene glycol diether, end blocked derivates of polyethylene glycol, polyethylene glycol monoether, polyethylene glycol diether, and combinations thereof.
20. The method of claim 11 wherein purifying comprises a process selected from the group consisting of short path distillation, thin film evaporation, wiped film evaporation, and adsorption to an inert adsorbent.
21. A method of preparing 2,5-(hydroxymethyl)furaldehyde comprising the steps of:
i) combining a fructose source, an acid catalyst, a first organic solvent, and a second organic solvent that is non miscible with the first organic solvent to provide a reaction mixture, the first and second organic solvents being selected so that the second organic solvent preferentially dissolves 2,5-(hydroxymethyl)furaldehyde relative to the first organic solvent;
ii) heating said reaction mixture to a temperature and for a time sufficient to promote a dehydration reaction of fructose in said fructose source to form a product mixture with a first immiscible phase and a second immiscible phase; and iii) isolating 2,5-(hydroxymethyl)furaldehyde from said second immiscible phase of said product mixture.
i) combining a fructose source, an acid catalyst, a first organic solvent, and a second organic solvent that is non miscible with the first organic solvent to provide a reaction mixture, the first and second organic solvents being selected so that the second organic solvent preferentially dissolves 2,5-(hydroxymethyl)furaldehyde relative to the first organic solvent;
ii) heating said reaction mixture to a temperature and for a time sufficient to promote a dehydration reaction of fructose in said fructose source to form a product mixture with a first immiscible phase and a second immiscible phase; and iii) isolating 2,5-(hydroxymethyl)furaldehyde from said second immiscible phase of said product mixture.
22. The method of claim 21 wherein said second organic solvent is selected from the group consisting of methyl isobutyl ketone, ethyl acetate and chloroform.
23. The method of claim 21 wherein said first organic solvent is dimethyl formamide.
24. The method of claim 42 wherein said second organic solvent has a Log P
value of from about 0.4 to about 3.4, and said first organic solvent has a Log P value of less than zero.
value of from about 0.4 to about 3.4, and said first organic solvent has a Log P value of less than zero.
25. The method of claim 47 wherein said second organic solvent has a Log P
value of from about 0.6 to about 2.7.
value of from about 0.6 to about 2.7.
26. The method of claim 47 wherein said first organic solvent has a Log P
value of from about -.075 to about -1.95.
value of from about -.075 to about -1.95.
27. A method of preparing an R-oxymethylfurfural ether of hydroxylmethylfurfural of the formula:
where R is selected from the group consisting of alkyl, cycloalkyl, allyl and aryl, comprising:
(i) combining a fructose source, an R-OH solvent, and an acid catalyst to form a reaction mixture;
(ii) heating said reaction mixture to a temperature and for a time sufficient to promote an acid-catalyzed dehydration reaction fructose in the fructose source and to form R-oxymethylfurfural in a product mixture; and (iii) Isolating the R-oxymethylfurfural from said product mixture.
where R is selected from the group consisting of alkyl, cycloalkyl, allyl and aryl, comprising:
(i) combining a fructose source, an R-OH solvent, and an acid catalyst to form a reaction mixture;
(ii) heating said reaction mixture to a temperature and for a time sufficient to promote an acid-catalyzed dehydration reaction fructose in the fructose source and to form R-oxymethylfurfural in a product mixture; and (iii) Isolating the R-oxymethylfurfural from said product mixture.
28. The method of claim 27 wherein the R-OH solvent is ethanol and the R-oxymethylfurfural is ethoxymethylfurfural.
29. The method of claim 27 wherein the acid catalyst is an acidic ion exchange resin.
30. A method of preparing levulinic acid comprising:
(i) combining a fructose source, at least one of polyethylene glycol and end capped polyethylene glycol, and an acid catalyst to form a reaction mixture;
(ii) heating said reaction mixture to a temperature and for a time sufficient to promote an acid-catalyzed dehydration reaction of fructose in the fructose source and to form levulinic acid in a product mixture; and (iii) isolating levulinic acid from said product mixture.
(i) combining a fructose source, at least one of polyethylene glycol and end capped polyethylene glycol, and an acid catalyst to form a reaction mixture;
(ii) heating said reaction mixture to a temperature and for a time sufficient to promote an acid-catalyzed dehydration reaction of fructose in the fructose source and to form levulinic acid in a product mixture; and (iii) isolating levulinic acid from said product mixture.
31. The method of claim 30 wherein the acid catalyst is an acidic ion exchange resin.
32. A method of preparing 2,5-bis-(hydroxymethyl)furan comprising:
heating a reaction mixture comprising 2,5-(hydroxymethyl)furaldehyde, a solvent, and a catalyst system comprising nickel and zirconium at a temperature, for a time, and at a pressure sufficient to promote reduction of the 2,5-(hydroxymethyl)furaldehyde to 2,5-bis-(hydroxymethyl)furan to produce a product mixture comprising 2,5-bis-(hydroxymethyl)furan.
heating a reaction mixture comprising 2,5-(hydroxymethyl)furaldehyde, a solvent, and a catalyst system comprising nickel and zirconium at a temperature, for a time, and at a pressure sufficient to promote reduction of the 2,5-(hydroxymethyl)furaldehyde to 2,5-bis-(hydroxymethyl)furan to produce a product mixture comprising 2,5-bis-(hydroxymethyl)furan.
33. The method of claim 32 wherein greater than 90% of the 2,5-(hydroxymethylfuraldehyde) is converted to 2,5-bis-(hydroxymethyl)furan.
34. The method of claim 32 wherein the temperature is between about 125° C
and about 175° C.
and about 175° C.
35. The method of claim 32 wherein the pressure is between about 1000 and about 1500 pounds per square inch.
36. The method of claim 32 wherein the time sufficient to promote reduction of the 2,5-(hydroxymethyl)furaldehyde to 2,5-bis-(hydroxymethyl)furan is less than about three hours.
37. The method of claim 32 wherein the solvent is one of ethyl acetate, acetate, methyl acetate, butyl acetate, isopropanol, and butanol.
38
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA2725173A CA2725173C (en) | 2004-12-10 | 2005-12-09 | Processes for the preparation and purification of hydroxymethylfuraldehyde and derivatives |
| CA2725803A CA2725803C (en) | 2004-12-10 | 2005-12-09 | Processes for the preparation and purification of hydroxymethylfuraldehyde and derivatives |
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US63540604P | 2004-12-10 | 2004-12-10 | |
| US60/635,406 | 2004-12-10 | ||
| US11/070,063 | 2005-03-02 | ||
| US11/070,063 US7393963B2 (en) | 2004-12-10 | 2005-03-02 | Conversion of 2,5-(hydroxymethyl)furaldehyde to industrial derivatives, purification of the derivatives, and industrial uses therefor |
| PCT/US2005/044598 WO2006063220A2 (en) | 2004-12-10 | 2005-12-09 | Preparation of 2,5-(hydr0xymethyl)furaldehyde (hmf) , derivatives thereof and levulinic acid from fructose as well as preparation of 2 , 5-bis- (hydroxymethyl) furan from 2 , 5- (hydroxymethyl) furaldehyde |
Related Child Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA2725173A Division CA2725173C (en) | 2004-12-10 | 2005-12-09 | Processes for the preparation and purification of hydroxymethylfuraldehyde and derivatives |
| CA2725803A Division CA2725803C (en) | 2004-12-10 | 2005-12-09 | Processes for the preparation and purification of hydroxymethylfuraldehyde and derivatives |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2590082A1 true CA2590082A1 (en) | 2006-06-15 |
| CA2590082C CA2590082C (en) | 2012-03-27 |
Family
ID=36177865
Family Applications (6)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA2590082A Active CA2590082C (en) | 2004-12-10 | 2005-12-09 | Processes for the preparation and purification of hydroxymethylfuraldehyde and derivatives |
| CA2691155A Active CA2691155C (en) | 2004-12-10 | 2005-12-09 | Coating composition comprising 2,5-bis(hydroxymethyl) tetrahydrofuran |
| CA2725803A Active CA2725803C (en) | 2004-12-10 | 2005-12-09 | Processes for the preparation and purification of hydroxymethylfuraldehyde and derivatives |
| CA2590123A Active CA2590123C (en) | 2004-12-10 | 2005-12-09 | Conversion of 2,5-(hydroxymethyl) furaldehyde to industrial derivatives, purification of the derivatives, and industrial uses therefor |
| CA2725173A Active CA2725173C (en) | 2004-12-10 | 2005-12-09 | Processes for the preparation and purification of hydroxymethylfuraldehyde and derivatives |
| CA2742630A Active CA2742630C (en) | 2004-12-10 | 2005-12-09 | Method for preparing 2,5-furandialdehyde |
Family Applications After (5)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA2691155A Active CA2691155C (en) | 2004-12-10 | 2005-12-09 | Coating composition comprising 2,5-bis(hydroxymethyl) tetrahydrofuran |
| CA2725803A Active CA2725803C (en) | 2004-12-10 | 2005-12-09 | Processes for the preparation and purification of hydroxymethylfuraldehyde and derivatives |
| CA2590123A Active CA2590123C (en) | 2004-12-10 | 2005-12-09 | Conversion of 2,5-(hydroxymethyl) furaldehyde to industrial derivatives, purification of the derivatives, and industrial uses therefor |
| CA2725173A Active CA2725173C (en) | 2004-12-10 | 2005-12-09 | Processes for the preparation and purification of hydroxymethylfuraldehyde and derivatives |
| CA2742630A Active CA2742630C (en) | 2004-12-10 | 2005-12-09 | Method for preparing 2,5-furandialdehyde |
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